Photoacid generators and photoresists comprising same

Abstract

This invention relates to new photoacid generator compounds and photoresist compositions that comprise such compounds. In particular, the invention relates to photoacid generator compounds that generate an anthracene acid upon exposure to activating radiation, particularly anthracene sulfonic acids such as acids that include 9,10-dialkoxyanthracene-2-sulfonate moieties. Positive- and negative-acting chemically amplified resists that contain such PAGs and that are imaged with I-line (365 nm) radiation are particularly preferred.

What is claimed is:  
     
       1. A positive-acting photoresist composition comprising: 
       a resin binder and a photoacid generator compound in an amount sufficient to permit development of an exposed coating layer of the composition,  
       the resin binder selected from the group consisting of 1) a copolymer of a vinyl phenol and alkyl acrylate; 2) an acetal or ketal resin; 3) a polymer containing styrene and/or hydroxystyrene units; or 4) a polymer containing t-butyl acrylate units,  
       the photoacid generator generating an alkoxy anthracene sulfonate acid upon exposure to activating radiation, and is a compound of Formulae I, II, III, IV, VI, VIII, IX, XI, XIA, XIB, XII, XIIA or XIIB as those formulae are defined below:                    
       wherein R 1  and R 2  are each independently selected from the group consisting of halo, hydroxy, nitro, cyano, sulfonyl, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aminoalkyl, optionally substituted alkylthio, optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted aryloxy, optionally substituted aralkyl, optionally substituted alkanoyl, optionally substituted carbocyclic aryl, optionally substituted heteroaromatic or heteroalicyclic;  
       R 3  and R 4  are the same or different and are selected from the same group as defined for R 1  and R 2  above, with at least one of R 3  and R 4  being optionally substituted alkoxy;  
       m and n are each independently an integer of from 0 to 5;  
       o and p are each independently an integer of 0 or greater, wherein the sum of o and p is greater than zero and 8 or less;                    
       wherein R 1 , R 2 , R 3 , R 4 , o and p are each as defined above for Formula I; and m and n are each independently an integer from 0 to 7;                    
       wherein R 3 , R 4 , o and p are the same as defined in Formula I above; and  
       R 5  and R 6  are independently optionally substituted alkyl, optionally substituted alkoxy, or optionally substituted alkylthio;                    
       wherein R 3 , R 4 , o and p are the same as defined in Formula I above; and  
       R 5  and R 6  are the same as defined in Formula III above;                    
        wherein R 1 , R 3 , R 4 , p and o are the same as defined in Formula I above;  
        m is an integer from 0 to 4; and  
        z is an integer from 1 to 6;                    
        wherein each R 3 , R 4 , p and o are the same as defined in Formula I above;                    
        wherein each R 3 , R 4 , p and o are the same or different and are the same as defined in Formula I above;                    
        wherein R 3 , R 4 , p and o are the same as defined in Formula I above;  
        R 8  is the same as defined for R 1  in Formula I above;  
        r is an integer of from 0 to 5; and  
        each Alk is the same or different optionally substituted alkyl; or  
        each Alk may be taken together and form a C 2-8  alkylene or alkenylene chain and thereby form a ring with the sulfur cation;                    
        wherein all substituents are as defined in Formula XI above, except that r is an integer from 0 to 7;                    
        wherein all substituents are as defined in Formula XI above, except that r is an integer from 0 to 9;                    
        wherein R 3 , R 4 , p and o are the same as defined in Formula I above;  
        R 8  and r are the same as defined in Formula XI above;  
        each Alk is the same or different optionally substituted alkyl; or  
        each Alk may be taken together and form a C 2-8  alkylene or alkenylene chain and thereby form a ring with the sulfur cation;                    
        wherein all substituents are as defined in Formula XII above, except that r is an integer from 0 to 7;                    
        wherein all substituents are as defined in Formula XII above, except that r is an integer from 0 to 9.  
     
     
       2. The positive-acting photoresist composition of  claim 1  wherein the anthracene group of Formula II has an additional —SO 3  moiety, and the sum of p and o is 8 or less. 
     
     
       3. The positive-acting photoresist composition of  claim 1  wherein the anthracene group of Formula XIA has an additional —SO 3  moiety, and the sum of p and o is 8 or less. 
     
     
       4. The positive-acting photoresist composition of  claim 1  wherein the anthracene group of Formula XIB has an additional —SO 3  moiety, and the sum of p and o is 8 or less. 
     
     
       5. The positive-acting photoresist composition of  claim 1  wherein the anthracene group of Formula XII has an additional —SO 3  moiety, and the sum of p and o is 8 or less. 
     
     
       6. The positive-acting photoresist composition of  claim 1  wherein the anthracene group of Formula XIIA has an additional —SO 3  moiety, and the sum of p and o is 8 or less. 
     
     
       7. The positive-acting photoresist composition of  claim 1  wherein the anthracene group of Formula XIIB has an additional —SO 3  moiety, and the sum of p and o is 8 or less. 
     
     
       8. An article of manufacture having on at least one surface a coating layer of the positive-acting photoresist composition of  claim 1 . 
     
     
       9. An article of manufacture comprising a microelectronic wafer that has on at least one surface a coating layer of a positive-acting photoresist of  claim 1 . 
     
     
       10. An article of manufacture comprising a printed circuit board substrate that has on at least one surface a positive-acting coating layer of a photoresist of  claim 1 . 
     
     
       11. The article of  claim 10  wherein the printed circuit board substrate is a copper clad laminate. 
     
     
       12. A method for forming a photoresist relief image on a substrate comprising: 
       (a) applying a coating layer of a negative-acting photoresist composition on a substrate; and  
       (b) exposing the photoresist coating layer to patterned activating radiation and developing the exposed photoresist layer to provide a relief image; and  
       wherein the negative-acting photoresist composition comprises:  
       a resin binder and a photoacid generator compound in an amount sufficient to permit development of an exposed coating layer of the composition,  
       the photoacid generator generating an alkoxy anthracene sulfonate acid upon exposure to activating radiation, and selected from the group consisting of diaryliodonium salts, diphenyliodonium salts, dinaphthyliodonium salts, N-oxyimidosulfonates, phenolic sulfonates, benzylic sulfonates, disulfones, diazosulfones, triarylsulfonium salts, aryl(dialkyl)sulfonium salts, phenacylsulfonium salts, naphthylacylsulfonium salts, and acenaphthylacylsulfonium salts, all of which may be optionally substituted  
       wherein the negative-acting photoresist coating layer is exposed to radiation having a wavelength selected from the group consisting of about 248 nm, 300 nm, 365 nm and about 435 nm.  
     
     
       13. An article of manufacture comprising a microelectronic wafer that has on at least one surface a coating layer of a negative-acting photoresist, 
       wherein the negative-acting photoresist comprises:  
       a resin binder and a photoacid generator compound in an amount sufficient to permit development of an exposed coating layer of the composition,  
       the photoacid generator generating an alkoxy anthracene sulfonate acid upon exposure to activating radiation, and selected from the group consisting of diaryliodonium salts, diphenyliodonium salts, dinaphthyliodonium salts, N-oxyimidosulfonates, N-oxyiminosulfonate, phenolic sulfonates, benzylic sulfonates, disulfones, diazosulfones, triarylsulfonium salts, aryl(dialkyl)sulfonium salts, phenacylsulfonium salts, naphthylacylsulfonium salts, and acenaphthylacylsulfonium salts, all of which may be optionally substituted.  
     
     
       14. An article of manufacture comprising a printed circuit board substrate that has on at least one surface a coating layer of a negative-acting photoresist, 
       wherein the negative-acting photoresist comprises:  
       a resin binder and a photoacid generator compound in an amount sufficient to permit development of an exposed coating layer of the composition,  
       the photoacid generator generating an alkoxy anthracene sulfonate acid upon exposure to activating radiation, and selected from the group consisting of diaryliodonium salts, diphenyliodonium salts, dinaphthyliodonium salts, N-oxyimidosulfonates, N-oxyiminosulfonate, phenolic sulfonates, benzylic sulfonates, disulfones, diazosulfones, triarylsulfonium salts, aryl(dialkyl)sulfonium salts, phenacylsulfonium salts, naphthylacylsulfonium salts, and acenaphthylacylsulfonium salts, all of which may be optionally substituted.  
     
     
       15. The article of  claim 14  wherein the printed circuit board substrate is a copper clad laminate. 
     
     
       16. A photoacid generator compound that can generate an anthracene sulfonate acid upon exposure to activating radiation, the photoacid generator compound generating an alkoxy anthracene sulfonate acid upon exposure to activating radiation being a compound of Formulae III, VI, VII, IX, XII, XIIA or XIIB as those formulae are defined below:                    
       wherein R 3  and R 4  are each independently a non-hydrogen substituent selected from the group consisting of halo, hydroxy, nitro, cyano, sulfonyl, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aminoalkyl, optionally substituted alkylthio, optionally substituted alkylsulfonyl, optionally substituted alkylsulfonyl, optionally substituted aryloxy, optionally substituted aralkyl, optionally substituted alkanoyl, optionally substituted carbocyclic aryl, optionally substituted heteroaromatic or heteroalicyclic, with at least one of R 3  and R 4  being optionally substituted alkoxy;  
       o and p are each independently an integer of 0 or greater, wherein the sum of o and p is greater than zero and 8 or less; and  
       R 5  and R 6  are independently optionally substituted alkyl, optionally substituted alkoxy, or optionally substituted alkylthio;                    
       wherein R 3 , R 4 , p and o are the same as defined in Formula III above;  
       each R′ is independently the same as defined for R 3  and R 4  in Formula III above;  
       m is an integer from 0 to 4; and  
       z is an integer from 1 to 6;                    
       wherein each R 3 , R 4 , p and o are the same as defined in Formula III above;                    
       wherein each R 3 , R 4 , p and o are the same or different and are the same as defined in Formula III above;                    
        wherein R 3 , R 4 , p and o are the same as defined in Formula III above;  
        R 8  is the same as defined for R′ in Formula I above;  
        r is an integer of from 0 to 5;  
        each Alk is the same or different optionally substituted alkyl; or  
        each Alk may be taken together and form a C 2-8  alkylene or alkenylene chain and thereby form a ring with the sulfur cation;                    
        wherein all substituents are as defined in Formula XII above, except that r is an integer from 0 to 7;                    
        wherein all substituents are as defined in Formula XII above, except that r is an integer from 0 to 5.  
     
     
       17. The photoacid generator of  claim 16  wherein the anthracene group of Formula XII has an additional —SO 3  moiety, and the sum of p and o is 8 or less. 
     
     
       18. The photoacid generator of  claim 16  wherein the anthracene group of Formula XIIA has an additional —SO 3  moiety, and the sum of p and o is 8 or less. 
     
     
       19. The photoacid generator of  claim 16  wherein the anthracene group of Formula XIIB has an additional —SO 3  moiety, and the sum of p and o is 8 or less.